Electrochemical cells and batteries

ABSTRACT

Membraneless electrochemical cells and batteries are disclosed. The cells comprise electrolyte solutions that are not miscible. The cells and batteries disclosed herein may be used to deliver electricity to process applications.

RELATED APPLICATIONS

This application is a U.S. national stage application under 35 U.S.C.371 of PCT international patent application PCT/US16/66421, filed Dec.13, 2016, which claims the benefit of U.S. Provisional PatentApplication Ser. No. 62/419,512, filed Nov. 9, 2016, U.S. ProvisionalPatent Application Ser. No. 62/348,607, filed Jun. 10, 2016, and U.S.Provisional Patent Application Ser. No. 62/267,152, filed Dec. 14, 2015.The contents of each of the aforementioned applications are incorporatedherein by reference in their entirety.

BACKGROUND

Liquid batteries, whether flow or no-flow, are known in the art and workon the same principles as solid batteries, except the electrolyte isliquid. Such batteries are comprised of electrochemical cells which arebased on reduction-oxidation chemistry. Oxidation occurs on the anodeside of the cell and reduction on the cathode side. The solvents used inelectrochemical cells are varied. In many circumstances, aqueoussolutions are used on both sides of an electrochemical cell with eachside (cathode side and anode side) in contact with an electrode (i.e.,the cathode and anode respectively). The electrodes of the two-halfcells are placed in electrical contact to allow for current to flow. Tomaintain charge balance, an electrochemical cell must also allow for thepassage of ions. In elementary batteries, this is done with a saltbridge separating the cathode solution from the anode solution. Thebridge prevents mixing of the two solutions. If the solutions were tomix, the half-cells could be destroyed by direct chemical reaction.

As with most batteries, flow batteries typically deploy a membraneseparating the anode electrolyte from the cathode electrolyte. The roleof the membrane is to allow for the exchange of ions but without mixingof the electrolyte solutions and thus the membrane preserves theelectrochemical cell. In addition, for flow batteries, the electrolyteis continuously replaced (thus the terminology “flow”). Membranes,however, are a major weakness in batteries generally and in flowbatteries in particular because they tend to degrade with time(especially in the presence of strong bases and acids) and are costly.

Membraneless flow batteries have been reported in the literature, butthey too suffer from significant drawbacks. Such membraneless batteriesare often termed “laminar” flow batteries because they rely on laminarflow to maintain separation of the analyte and the catholyte. Aconventional laminar flow battery does not have a membrane and operatesbecause of the slow rate of mixing of the two fluids in the laminarregime. However, mixing does occur, resulting in waste and, if allowedto progress, the mixing will short-circuit the battery. Membranelesssystems have been proposed in which the electrolytes are selected on thebasis of their pH. However, such systems can produce a precipitate atthe interface between the electrolytes. Accordingly, there remains aneed for further contributions in this area of technology.

SUMMARY

In one aspect of the disclosure, an electrochemical cell is providedcomprising a cathode, an anode adjacent the cathode at a distance, afirst polar electrolyte solution in contact with the cathode anddisposed within the distance, a second polar electrolyte solution incontact with the anode and disposed within the distance, wherein thefirst and second electrolyte solutions are in contact with each otherand are immiscible, and wherein there is no membrane in between thefirst and second electrolyte solutions.

In a further aspect of the disclosure, an electrochemical cell isprovided comprising a cathode, an anode adjacent the cathode at adistance, a first polar acidic electrolyte solution in contact with thecathode and disposed within the distance, a second polar neutralelectrolyte solution in contact with the anode and disposed within thedistance, wherein the first and second electrolyte solutions are incontact with each other and are immiscible, and wherein there is nomembrane in between the first and second electrolyte solutions.

In an additional aspect of the disclosure, an electrochemical cell isprovided comprising a cathode, an anode adjacent the cathode at adistance, a first electrolyte solution in contact with the cathode anddisposed within the distance, a second electrolyte solution in contactwith the anode and disposed within the distance, wherein the first andsecond electrolyte solutions are in contact with each other and areimmiscible, and wherein there is no membrane in between the first andsecond electrolyte solutions.

In a further aspect of the disclosure, electrochemical cells areprovided comprising a first conducting material adjacent at a distanceto a second conducting material, an anode in contact with the secondconducting material, a second electrolyte solution in contact with theanode and the first conducting material disposed within the distance,and a first electrolyte solution disposed within the distance in contactwith the first conducting material, wherein the first and secondelectrolyte solutions are not miscible; the first and second conductingmaterial are in electrical contact, and wherein metal ions are in thefirst electrolyte solution.

In a still further aspect of the disclosure, electrochemical batteriesare provided comprising one or more electrochemical cells of thedisclosure.

In a further aspect of the disclosure, methods for deliveringelectricity to process applications from electrochemical cells of thedisclosure are provided.

In yet an additional aspect of the disclosure, methods for deliveringelectricity to process applications from electrochemical batteries ofthe disclosure are provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic block diagram of an embodiment of anelectrochemical cell according to the present disclosure;

FIG. 2A is a schematic block diagram of an embodiment of anelectrochemical cell according to the present disclosure;

FIG. 2B is a schematic block diagram of an embodiment of anelectrochemical cell according to the present disclosure

FIG. 3A is a top-down view of an electrochemical battery embodiment ofthe disclosure.

FIG. 3B a top-down view of an electrochemical battery embodiment of thedisclosure

FIG. 3C a top-down view of an electrochemical battery embodiment of thedisclosure

FIG. 3D is a side view of FIG. 3A.

FIG. 3E is a side view of FIG. 3B.

FIG. 3F is a side view of FIG. 3C.

FIG. 4 is a schematic of an embodiment of a series of electrochemicalcells of the disclosure.

FIG. 5 is a schematic of an embodiment of an electrochemical cell of thedisclosure.

FIG. 6 is a schematic of an embodiment of an electrochemical cell of thedisclosure.

DETAILED DESCRIPTION

The electrochemical cells and batteries of the disclosure operatewithout the need for membranes or other devices to separate the firstelectrolyte solution (at the cathode) from the second electrolytesolution (at the anode). When the terms “membraneless” or “without amembrane” or “wherein there is no membrane” or words to that effect areused, what is meant is that there is no membrane or other kind ofseparator between the first and second electrolyte solutions (and thirdelectrolyte solutions in those embodiments). For example, whereastypical membranes are proton exchange membranes, a separator can operateby separating the anode and cathode of a battery, for example, andpermit electrolyte ions to pass to maintain charge neutrality, but notthe reactants associated with oxidation or reduction such as is used inthe electrochemical cells of the disclosure. The electrochemical cellsof the disclosure operate without any such membrane or separator betweenthe electrolyte solutions, but a separator may be employed, for example,in between such cells in a voltaic pile. In typical cells of thedisclosure, the first electrolyte solution, is an aqueous solution andthe second electrolyte solution is an alcoholic solution. The solutionat each electrode must contain the necessary components so thatoxidation-reduction will occur, thus generating electricity.

For example, in one embodiment, at the cathode, vanadium undergoesreduction from V⁵⁺ to V⁴⁺. In that embodiment, at the anode, zinc isoxidized from Zn(s) to Zn²⁺. To enable the flow of positively chargedions, a methanol solvent with zinc solid on the anode side is furthercharged with ammonium chloride. The ammonium chloride dissolves anddissociates sufficiently to provide NH₄ ⁺ in solution as a positivelycharged ion and Cl⁻ as a negatively charged ion. On the cathode side,positively charged ions are provided by adding both sulfuric acid(H₂SO₄) and sodium sulfate (Na₂SO₄) to an aqueous V⁵⁺ solution. Thedissolution and dissociation into H⁺ and Na⁺ provides positively chargedions and SO₄ ²⁻ as a negatively charged ion on the cathode side of theelectrochemical cell. In addition, the sodium sulfate prevents themixing of the first and second electrolyte solutions and maintains theirimmiscibility. Further, since water is denser than methanol, buoyancyforces cause the methanol solution to layer on top of the denser aqueoussolution. This layering of immiscible fluids (salt water is immisciblewith methanol or ethanol) effectively and advantageously eliminates theneed for a membrane for separation. Such embodiments may be configuredfor flow or for no-flow operation as described further herein. Further,in such embodiments the zinc may be in contact with a conductingmaterial such as conducting carbon and the cathode solution may also bein contact with such a conducting material.

Electrochemical batteries of one or more cells, including greater thanone cell, may be prepared by combining electrochemical cells of thedisclosure in parallel or in series. Examples include a voltaic pile ofcells. Separators or interconnects may be used to separate adjacentcells to prevent short-circuiting such batteries but still provide forelectrical communication. Such cells and batteries may be used todeliver or receive electricity to process applications such as solarfarms and wind farms, vehicles, electrical grids, household appliances,consumer products, and toys.

According to many embodiments of the present disclosure, and as shown inFIG. 1, an electrochemical cell 10 is provided. The electrochemical cell10 includes a cathode 12 and an anode 14 separated by a firstelectrolyte solution 20 and a second electrolyte solution 22 such thatthe first electrolyte solution 20 is in contact with the cathode 12 andsuch that the second electrolyte solution 22 is in contact with theanode 14. The first electrolyte solution 20 and the second electrolytesolution 22 are immiscible and in contact with each other and thus canenable ion and electron exchange (e.g., H⁺ and e−) between the anode 14and the cathode 12. Each cell 10 may be electrically connected to a load16 by a circuit 18 to enable a current flow via the circuit. Note thatthe vertical lines connecting the electrolyte solutions and the cathodeand anode electrodes in the schematic are not conduits but are merely toaid in the viewing of the schematic.

In certain embodiments, the first electrolyte solution 20 may be apositive electrolyte or catholyte, and the second electrolyte solution22 may be a negative electrolyte or anolyte (and immiscible). In manyembodiments, the densities of the first electrolyte solution and thesecond electrolyte solution are different with the first electrolytesolution 20 being denser than the second electrolyte solution 22 suchthat when the cell 10 is oriented vertically with cathode 12 at thebottom, the buoyancy effect causes the second electrolyte solution 22 tolayer above the first electrolyte solution 20.

In many embodiments, the cell 10 may optionally be configured to run inflow mode so as to support a flow battery for example. In such abattery, electrolyte solutions are provided to the cell during theoperation of the battery continuously during operation. For example, thefirst electrolyte solution 20 and the second electrolyte solution 22 mayflow into the cell 10 and between the cathode 12 and the anode 14 from afirst source, such as a tank, 30, or other suitable storage device, anda second source, such as a tank, 32, or other suitable storage device,respectively, as shown in FIG. 1 via conduits 21 and 25 respectively.The first electrolyte solution 20 and second electrolyte solution 22 mayfurther flow out of the cell 10 via conduits 23 and 27 respectively.They may be directed to waste or to other tanks. In some embodiments,flow could be reversed from said other tanks to recharge cell 10. Theflows may be generated by pumps 50, 52 or by capillarity, reverseosmosis, a ratchet, swelling pressure, or gravity. The flows of thefirst electrolyte solution 20 and the second electrolyte solution 22 maybe maintained within a laminar flow regime. In alternative embodiments,the first electrolyte solution 20 and the second electrolyte solution 22may not flow through the cell 10 but may be replaceable.

In these and other embodiments of the disclosure both the first andsecond electrolyte solutions may be polar and of different densities. Inmany examples, the first polar electrolyte solution contains water and asalt. In some embodiments, the solution is saturated with respect to thesalt. Examples of salts include metal halides or ammonium salts such assodium chloride, magnesium chloride, lithium chloride and ammoniumchloride. Other salts include sodium sulfate, calcium sulfate, potassiumsulfate, and ammonium sulfate among others. The first polar electrolytesolution or the second polar electrolyte solution, or both, may beneutral or made basic, such as by addition of sodium hydroxide,potassium hydroxide, calcium hydroxide, or a combination thereof.

In such embodiments, the second electrolyte solution may contain analcohol. Other constituents may include a salt, such as a metal halideor ammonium salt, examples being sodium chloride, magnesium chloride,lithium chloride and ammonium chloride. Suitable alcohols for use in thesecond electrolyte solution include methanol and ethanol.

Cathodes and anodes of the various embodiments may be selected fromsuitable materials. Example of suitable cathodes, include steel, carbonsuch as in the graphite allotrope of carbon, and carbon impregnated witha metal. Conducting carbon cloth, for example, is a suitable cathode formany embodiments and is a conducting material. Suitable anodes includemetals such as platinum, zinc, lithium, nickel, calcium, magnesium oraluminum.

When an electrolyte solution is prepared, typically an electrolyte,often a solid, is disposed within a solvent which then becomes anelectrolyte solution. For example, when an electrolyte is disposedwithin a solvent where it can dissolve, the dissolution of theelectrolyte solid will create ions and, if they dissociate sufficiently,the solvent becomes an electrolyte solution. In addition, othercomponents are added to the solvent so that oxidation will occur at theanode and reduction at the cathode. Examples of such a component is zincmetal. When added at the anode of an operating electrochemical cell,zinc will oxidize to Zn²⁺. On the cathode side, one such componentexample is NH₄VO₃ which dissolves and dissociates to produce V⁵, whichwill be reduced to V⁴⁺ in an operating electrochemical cell. In manysuch embodiments of the disclosure, the first electrolyte solutioncomprises a component which dissociates into an ion selected from ClO⁻,Fe³⁺, V⁵⁺, Br₂, and S₂O₈ ²⁻, which ions are reduced at the cathode. Inthese and other embodiments, the second electrolyte solution comprises acomponent which oxidizes into an ion selected from Li⁺, Ca²⁺, Al³⁺,Mg²⁺, V²⁺, Zn²⁺, SiO₃ ²⁺, [Zn(CN)₄]²⁻, and [Zn(OH)₄]²⁻, which ionsresult from oxidation at the anode.

In these and other embodiments, the first electrolyte solution may bepolar and acidic and the second electrolyte solution may be polar andneutral and the first and second electrolyte solutions are of differentdensities. In such embodiments, a strong acid, such as sulfuric acid(e.g., 1M) may be used to make the first polar electrolyte solutionacidic. With respect to the electrolytes, a salt such as sodium sulfateor sodium chloride may be present in the first electrolyte solution andammonium chloride in the second electrolyte solution. The solution maybe saturated with respect to the salt selected. The second polar andneutral electrolyte solution in such embodiments comprises a solventsuch as an alcohol. Examples of alcohols that may act as solvents hereininclude methanol and ethanol.

In some embodiments, the anode is aluminum and the cathode is carbon orsteel, the first electrolyte solution contains water and ClO⁻, and thesecond electrolyte solution contains ethanol or methanol. In suchembodiments, for example, each electrolyte contains a base such as NaOH,and a salt, LiCl which results in immiscible electrolyte solutions. Thevoltage supplied by such an electrochemical cell is between 1.5 and 2.1volts. Such an electrochemical cell may create amperages of betweenabout 0.1 and about 0.4 amps including about 0.2 and about 0.3 amps.Examples of components providing ClO⁻ include Na(ClO) and Ca(ClO)₂. Insuch a cell, ClO⁻ will be reduced at the cathode according to equation1:ClO⁻+H₂O+2e ⁻→Cl⁻(aq)+2OH⁻(aq)  EQ. 1The second electrolyte may contain a component that is a metal thatoxidizes, such as aluminum oxidizing to Al³⁺as per equation 2:Al(s)→Al³⁺(aq)+3e ⁻  EQ.2Another anode choice may be magnesium which oxidizes per equation 3:Mg(s)→Mg²⁺(aq)+2e ⁻  EQ. 3or Vanadium which oxidizes per equation 4:V(s)→V²⁺(aq)+2e ⁻  EQ. 4

In certain embodiments, the first electrolyte solution 20 may include asolution of diatomic bromine (Br₂), tetraalkyl ammonium bromide salt andethyl acetate, and the second electrolyte solution 22 may include anaqueous solution including hydrogen bromide (hydrobromic acid).Alternatively, the first electrolyte solution 20 may be denser than thesecond electrolyte solution 22. In such embodiments, a reductant 26,such as shown in FIG. 1, may optionally be supplied to the anode 14 viaconduit 29 to donate electrons to the second electrolyte solution 22. Inat least one embodiment, the reductant may be hydrogen (H₂) gas, and theanode 14 via conduit 29 may be comprised of any suitable chargecollector including, for example, a Platinum catalyst. In such anembodiment, the chemical reaction at the anode 14 is:H₂−2e ⁻→2H⁺ (in aqueous solution for example)  EQ. 5The cathode 12 may be comprised of any suitable material including, forexample, graphite. The current flow in the circuit 18 enables areduction reaction at the cathode 12. The first electrolyte solution 20may be reduced as:Br₂+2e ⁻→2Br⁻ (in ethyl acetate for example)  EQ. 6

In other certain embodiments, a cell 10 may include first electrolytesolution 20 and second electrolyte solution 22. In at least oneembodiment, the first electrolyte solution 20 may contain liquid brominehaving a density of approximately 3.12 g/cm³. The second electrolytesolution 22 may contain HBr in H₂O which is less dense. In such anembodiment, because the second electrolyte solution 22 is less densethan the first electrolyte solution 20, the buoyancy effect will causethe second electrolyte solution 22 to layer above the first electrolytesolution 20. Further, because HBr in water is immiscible with liquidbromine, the layers of the first electrolyte solution 20 and secondelectrolyte solution 22 will not mix significantly at the interfacetherebetween. Accordingly, the anode 14 in contact with the secondelectrolyte solution 22 may be disposed above the cathode 12 in contactwith the first electrolyte solution 20. Consequently, the reaction atthe anode 14 is the same as shown in EQ. 5, and the reaction at thecathode 12 is the same as shown in EQ. 6.

In electrochemical batteries of the disclosure, it may be useful tostack more than one electrochemical cells. The stacking of cells may beenabled, for example, by the use of three or more immiscible fluidshaving three or more different densities. In such embodiments, a secondcathode opposite the first cathode at a second distance from the anodeis provided and a third electrolyte solution in contact with the secondcathode and the second electrolyte solution is further provided whereinthe third and second electrolyte solutions are in contact with eachother and are immiscible, and wherein there is no membrane in betweenthe third and second electrolyte solutions. The third electrolytesolution may be polar and will be a greater density than the first twoelectrolyte solutions. An example of a third electrolyte solution thatis denser than water is one that contains propylene carbonate as asolvent. The third electrolyte solution may contain a salt and may besaturated with respect to that salt. Batteries with such cells may beconfigured in flow or no flow mode.

In at least one embodiment according to the present disclosure, as shownin FIG. 2A, a battery may include a cell 11 including a firstelectrolyte solution 20, a second electrolyte solution 22, and a thirdelectrolyte solution 24. In such an embodiment, the cell 11 includes onecathode 12 operating with two anodes 14 to generate electricity suppliedto the load 16 via circuit 18. In such an embodiment, the thirdelectrolyte solution 24 is denser than the first electrolyte solution 20and the second electrolyte solution 22. The third electrolyte solution24 is immiscible relative to the first electrolyte solution 20 and/orthe second electrolyte solution 22. Accordingly, the second electrolytesolution 20 is disposed in a layer above the first electrolyte solution22, and the first electrolyte solution 22 is disposed in a separatelayer above the third electrolyte solution 24. Optional tanks 30 and 32,acting as sources for electrolyte solutions, and pumps 50 and 52 (or bycapillarity, reverse osmosis, a ratchet, swelling pressure, or gravity),may be used to deliver electrolyte solutions to the cell in flow mode,for example via conduits 21 and 25 respectively. The first electrolytesolution 20 and second electrolyte solution 22 may further flow out ofthe cell 11 via conduits 23 and 27 respectively. They may be directed towaste or to other tanks. In some embodiments, flow could be reversedfrom said other tanks to recharge cell 11. In other embodiments, thecell can be arranged with a cathode on top and bottom and an anode inthe middle.

As shown in FIG. 2A, the third electrolyte solution 24 may be suppliedto the cell 11 from a third source 34 via conduit 31 with pump 54 (or bycapillarity, reverse osmosis, a ratchet, swelling pressure, or gravity)which may be used in flow mode. The third electrolyte solution 24 mayfurther flow out of cell 11 via conduit 33. This may be directed towaste or to another tank. In some embodiments, flow could be reversedfrom said another tank to recharge cell 11. In embodiments in which thethird electrolyte solution 24 flows through the cell 11, the thirdelectrolyte solution 24 may be directed to waste or to other tanks. Insome embodiments, flow could be reversed and from the other tanks torecharge the cells. Alternatively, the third electrolyte solution 24 maynot flow through the cell 11 but may be replaceable. Note that thevertical lines connecting the electrolyte solutions and the cathode andanode electrodes in the schematic are not conduits but are merely to aidin the viewing of the schematic.

In FIG. 2B, electrochemical cell 11 a is a three-layer system presentedwith two cathodes 12 and one anode 14. First electrolyte solution 20 isin contact with cathode 12 and second electrolyte solution 22 which inturn is in contact with anode 14 and third electrolyte solution 24.Cathode 12 is in contact with the third electrolyte solution 24 and load16 via circuit 18. An optional reductant (H₂ gas) 26 may supply the H₂to anode 14 via conduit 31 a. Flow tanks, conduits, and pumps (or bycapillarity, reverse osmosis, a ratchet, swelling pressure, or gravity)may be used to run electrochemical cell 11 a in flow mode and thus allowfor recharging. Note that the vertical lines connecting the electrolytesolutions and the cathode and anode electrodes in the schematic are notconduits but are merely to aid in the viewing of the schematic.

In at least one embodiment according to the present disclosure, thebatteries and cells of the disclosure may employ porous media tostabilize and enhance performance. The use of porous media affects someor all of the following characteristics of batteries and electrochemicalcells of the disclosure: wettability boundary conditions; no slip andslip boundary conditions; conductivity, including resistivity andfriction; dispersivity or mixing between adjacent fluids; porosity(e.g., relative volume for flow); tortuosity (e.g., length andcomplexity of trajectories); connectivity (e.g., species andelectrical); particle size distribution (e.g., packing); relativeconductivity (e.g., multiphase resistivity); multiscale (e.g., discretescale separation); surface absorptivity (e.g., double layercapacitance); surface reactivity (e.g., pseudo capacitance); diagenesis(e.g., dissolution or deposition); and swelling (e.g., interfacialforces). The porous media may include nanostructures or nanoparticles.Such porous media may be used, for example, at the cathode or anode.Examples of such porous media include micro- or nano-porous graphite.For example, in at least one embodiment according to the presentdisclosure, cell 10 may employ a nano-porous or micro-porousBr₂-saturated graphite cathode 12. Such a cathode 12 can be thought ofas a reduction cathode 12 that accepts electrons to form the reactionaccording to EQ. 4 at the Br₂-graphite interface. The graphite is porouswith desirably high specific surface area and is saturated with Br₂.

FIGS. 3A, 3B, and 3C show top-down views of embodiments of porous mediacarbon nanorods saturated with Br₂. FIGS. 3D, 3E, and 3F arecorresponding side views. In these Figures, carbon nanorods 202, 205,and 208 are disposed on surfaces 201, 204, and 207 respectively withinterstitial spaces containing liquid Br₂ 203, 206, and 209respectively. Water and HBr may be deployed on top of the surface madeby the top of the nanorods as illustrated in FIG. 4. Any conductingporous substrate with high specific surface area can be used instead ofcarbon nanorods. Further, graphite in varying forms can be used,including for example, powdered graphite.

In addition, as shown in FIG. 4, a side view of any of FIGS. 3A, 3B, and3C is provided. Anode 49, a platinum embedded carbon cloth, is separatedfrom the bromine-saturated carbon-nanorod cathode 42 shown as an arrayof nanorods, with the water and HBr fluid flowing through the middle 46.Liquid Br₂ fills the spaces 44 in between the nanorods. A conductingmaterial such as conducting carbon or steel 48 is in contact withnanorods 42 and Br₂ cavities 44. The Br₂ can be wicked up from areservoir without the need for a convective flow field and stillremaining at constant density.Br₂+2e ⁻→2Br⁻ (at graphite interface for example)  EQ. 7

The electrochemical cells may be used individually as batteries orcombined for use in a battery. Such batteries may be rechargeable.

In some embodiments, a first and second electrolyte solution are ofdifferent densities and immiscible due to the presence of a salt in thefirst electrolyte solution and are in contact without a membrane.Further, the cell is configured to run in a no flow mode. Batteries maybe made of such cells such as in parallel or series geometry and/or avoltaic pile. The electricity from such batteries may be delivered to aprocess application such as solar farms, wind farms, householdappliances, consumer goods, or toys.

Example 1 V/Zn Electrochemical Cell/Battery with Immiscible ElectrolyteSolutions without a Membrane

A no flow electrochemical cell/battery configured in accordance with theschematic of FIG. 5 (other than the flow portion of the schematic) wasprepared. The figure represents both an electrochemical cell and abattery with a battery being defined as containing one or moreelectrochemical cells. The cell/battery was made from acrylic. Aconducting carbon (graphite) cloth 58 was affixed to zinc-metalparticles 59 inside a neutral electrolyte solution of ammonium chloridein methanol 22 a. On the cathode side, a 1M sulfuric acid solution 20 acontaining on the order of 1% by mass sodium sulfate was used. Thecathode was prepared by adding solid NH₄VO₃ as the electrolyte. Thesolid dissolved readily in the acidic solution to provide V⁵⁺ insolution 20 a. As with the anode side, the cathode side contains acarbon (graphite) cloth 58. Both carbon cloths are electrically incontact through the Load 16 via circuit 18.

The cell/battery of FIG. 5 could be run in flow mode by attachingoptional tanks 30 and 32 and pumps 50 and 52 (or by capillarity, reverseosmosis, a ratchet, swelling pressure, or gravity) via conduits 21 and25 respectively. The outflow from the cell/battery 23 and 27 could berouted to waste or to an external tank so that recharge could occur byreversing polarities.

The electrochemical cell/battery generates 1.7 volts through thecombination of the anode and cathode reactions. On the anode side, theoxidation of zinc from Zn to Zn²⁺ was measured to be 0.7 volts whereasthe reduction of V⁵⁺ to V⁴⁺ generates a voltage of 1.0 with a totalcell/battery delivery of 1.7 volts at 0.33 A with a one ohm resistance.The vanadium is further reduced to V³⁺ and V²⁺ in further reactions.Although each solution is polar, the different electrolyte solutions areimmiscible. Further, they have different densities with the sulfuricacid solution being denser, and thus on the bottom and the less denseneutral methanol solution on top.

In other V/Zn embodiments, such electrochemical cells may be used toeach produce voltages from between about 1 and 2.5 volts includingbetween about 1 and 2 volts, between about 1 and 1.6 volts, betweenabout 1.6 and 1.8 volts and about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7,1.8, 1.9, or 2.0 volts. Other voltages are greater than 2 volts andinclude between about 2.1 and 2.3 volts including about 2.2 volts. Ifdesired, lower voltages may be delivered such as between about 0.5 and 1volt. The amps produced by the cells are typically greater than 0.25 Aincluding 0.33 amps and higher (with a one ohm resistance). The use ofthe word “about” herein is used to account for measurement errorassociated with measuring voltages or amps by those of ordinary skill inthe art using typical measuring devices of the art.

Example 2 Al/Hypochlorite Electrochemical Cell/Battery with ImmiscibleElectrolyte Solutions without a Membrane

A no flow electrochemical cell/battery configured in accordance with theschematic of FIG. 6 (other than the flow portion of the schematic) wasprepared. The figure represents both an electrochemical cell and abattery with a battery being defined as containing one or moreelectrochemical cells. The cell/battery was made in a glass beaker.Aluminum solid was used as anode 62 and electrically connected viacircuit 18 and Load 16 to cathode 63, conducting carbon cloth or steeldepending on the specific experiment. The anode was placed in anelectrolyte solution 22 b containing ethanol or methanol (multiple weretested), lithium chloride and sodium hydroxide. The cathode was placedin contact with an electrolyte solution 20 b containing NaClO orCa(ClO)₂ depending on the specific experiment, resulting in ClO⁻ iondissolved in a solution containing sodium hydroxide, lithium chloride,and water. Although each solution is polar, the different electrolytesolutions are immiscible. Further, they have different densities withthe hypochlorite solution being denser, and thus on the bottom and theless dense neutral alcohol (ethanol or methanol) solution on top. Thecell/battery of FIG. 6 could be run in flow mode by attaching optionaltanks 30 and 32 and pumps 50 and 52 (or by capillarity, reverse osmosis,a ratchet, swelling pressure, or gravity) via conduits 21 and 25respectively. The outflow from the cell/battery 23 and 27 could berouted to waste or to an external tank for recharge purposes viareversing polarity.

In no flow mode, such a cell/battery was measured to provide an initialoutput of over 2 volts with amperage of up to 0.3 amps at a 1 ohm load.

In the various descriptions above, electrochemical cells are stackedvertically. In alternative embodiments, adjacent electrochemical cells,for example, may be disposed in other orientations to make batteries.

A variety of embodiments according to the present disclosure arecontemplated. Such embodiments may be employed in a variety of methods,processes, procedures, steps, and operations as a means of providingelectrochemical cells and batteries. While the invention has beenillustrated and described in detail in the drawings and foregoingdescription, the same is to be considered as illustrative and notrestrictive in character, it being understood that only certainexemplary embodiments have been shown and described. Those skilled inthe art will appreciate that many modifications are possible in theexample embodiments without materially departing from this invention.Accordingly, all such modifications are intended to be included withinthe scope of this disclosure as defined in the following claims. Indeed,this disclosure is not intended to be exhaustive or to limit the scopeof the disclosure.

What is claimed is:
 1. An electrochemical cell comprising: a. a cathode;b. a metal anode adjacent the cathode at a distance; c. a firstelectrolyte solution comprising water, a metal chloride salt, and acomponent which dissociates into ions selected from ClO⁻, Fe³⁺, and S₂O₈²⁻, the first electrolyte solution in contact with the cathode anddisposed within the distance; and d. a second electrolyte solutioncomprising a solvent in contact with the anode and disposed within thedistance, wherein the first and second electrolyte solutions are incontact with each other and are immiscible, and wherein there is nomembrane in between the first and second electrolyte solutions.
 2. Theelectrochemical cell of claim 1, wherein the first electrolyte solutionand the second electrolyte solution each further comprise sodiumhydroxide.
 3. The electrochemical cell of claim 1 wherein the metalanode is aluminum.
 4. The electrochemical cell of claim 1 wherein themetal chloride salt is lithium chloride or sodium chloride.
 5. Theelectrochemical cell of claim 4, wherein the metal chloride salt islithium chloride salt.
 6. An electrochemical battery comprising one ormore electrochemical cells of claim
 1. 7. The electrochemical cell ofclaim 1, wherein the solvent in the second electrolyte solution is analcohol.
 8. The electrochemical cell of claim 7, wherein the alcohol inthe second electrolyte solution is methanol or ethanol.
 9. Theelectrochemical cell of claim 1 wherein the cell is configured to run ina flow mode.
 10. The electrochemical cell of claim 9 wherein the cathodeis graphite.
 11. The electrochemical cell of claim 1 wherein the cathodeis carbon or carbon impregnated with a metal.
 12. The electrochemicalcell of claim 1 wherein the second polar electrolyte solution is basicor neutral.
 13. The electrochemical cell of claim 1 wherein the firstelectrolyte solution comprises ClO⁻ ions.
 14. The electrochemical cellof claim 1 wherein the first electrolyte solution comprises Fe³⁺ ions.15. The electrochemical cell of claim 1 wherein the first electrolytesolution comprises S₂O₈ ²⁻ ions.
 16. The electrochemical cell of claim 1wherein the second electrolyte solution comprises a component whichoxidizes into an ion selected from Li⁺, Ca²⁺, Al³⁺, Zn²⁺, SiO₃ ²⁺,[Zn(CN)₄]²⁻, and [Zn(OH)₄]²⁻.
 17. A method of delivering electricityfrom an electrochemical cell of claim 1 to a process application. 18.The method of claim 17, wherein the process application is solar farms,wind farms, household appliances, consumer products, and toys.
 19. Amethod of delivering electricity from a battery of claim 1 to a processapplication.
 20. The method of claim 19, wherein the process applicationis solar farms, wind farms, household appliances, consumer products, andtoys.